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Louisville, KY, United States

Sharma V.K.,Florida Institute of Technology | Triantis T.M.,Institute of Physical Chemistry | Antoniou M.G.,Technical University of Denmark | He X.,University of Cincinnati | And 8 more authors.
Separation and Purification Technology

Cyanobacteria blooms pose an environmental hazard because of the release of water soluble toxic compounds, called cyanotoxins. Microcystins (MCs), hepatotoxic cyclic peptide toxins, are the most widespread cyanotoxins with microcystin-LR (MC-LR) the most common and toxic variant. Health effects of MCs have resulted in the need of using efficient treatment methods for the removal of this class of toxins in water supplies. While physical treatment methods can remove MCs at full or some extent from contaminated water, their function is primary separation of the whole toxins as intact molecules and further processing is required. On the other hand, chemical oxidation processes are a promising alternative treatment option due to the potential of complete destruction of the MCs, transformation to less toxic by-products, and even complete mineralization. MCs reactivity towards different conventional oxidants is strongly affected by water quality parameters like pH, DOC and oxidant dose. Although there is a general trend for MCs oxidation (ozone > permanganate > chlorine >>> chlorine-based oxidants), the selection of the appropriate oxidant for toxin elimination during water treatment should be assessed for each particular source of water. Although advanced oxidation processes are generally more effective on MCs degradation than conventional oxidation processes, scale-up studies are needed before these methods are considered as economically-feasible and practical sustainable alternatives in water treatment facilities. In this review, recent literature concerning treatment of MCs in water by conventional and advanced oxidation processes are reviewed and discussed in terms of the degree of degradation, reaction kinetics, identity and toxicity of oxidation by-products and possible degradation pathways. © 2011 Elsevier B.V. All rights reserved. Source

De La Cruz A.A.,U.S. Environmental Protection Agency | Hiskia A.,Greek National Center For Scientific Research | Kaloudis T.,Laboratory Supply Company | Chernoff N.,U.S. Environmental Protection Agency | And 11 more authors.
Environmental Sciences: Processes and Impacts

Cylindrospermopsin is an important cyanobacterial toxin found in water bodies worldwide. The ever-increasing and global occurrence of massive and prolonged blooms of cylindrospermopsin-producing cyanobacteria poses a potential threat to both human and ecosystem health. Its toxicity is associated with metabolic activation and may involve mechanisms that adversely affect a wide variety of targets in an organism. Cylindrospermopsin has been shown to be cytotoxic, dermatotoxic, genotoxic, hepatotoxic in vivo, developmentally toxic, and may be carcinogenic. Human exposure may occur through drinking water, during recreational activities and by consuming foods in which the toxin may have bioaccumulated. Drinking water shortages of sufficient quality coupled with growing human pressures and climate variability and change necessitate an integrated and sustainable water management program. This review presents an overview of the importance of cylindrospermopsin, its detection, toxicity, worldwide distribution, and lastly, its chemical and biological degradation and removal by natural processes and drinking water treatment processes. © 2013 The Royal Society of Chemistry. Source

Triantis T.M.,Institute of Physical Chemistry | Fotiou T.,Institute of Physical Chemistry | Kaloudis T.,Laboratory Supply Company | Kontos A.G.,Research Center for Energy Conversion And Storage | And 4 more authors.
Journal of Hazardous Materials

In an attempt to face serious environmental hazards, the degradation of microcystin-LR (MC-LR), one of the most common and more toxic water soluble cyanotoxin compounds released by cyanobacteria blooms, was investigated using nitrogen doped TiO 2 (N-TiO 2) photocatalyst, under UV-A, solar and visible light. Commercial Degussa P25 TiO 2, Kronos and reference TiO 2 nanopowders were used for comparison. It was found that under UV-A irradiation, all photocatalysts were effective in toxin elimination. The higher MC-LR degradation (99%) was observed with Degussa P25 TiO 2 followed by N-TiO 2 with 96% toxin destruction after 20min of illumination. Under solar light illumination, N-TiO 2 nanocatalyst exhibits similar photocatalytic activity with that of commercially available materials such as Degussa P25 and Kronos TiO 2 for the destruction of MC-LR. Upon irradiation with visible light Degussa P25 practically did not show any response, while the N-TiO 2 displayed remarkable photocatalytic efficiency. In addition, it has been shown that photodegradation products did not present any significant protein phosphatase inhibition activity, proving that toxicity is proportional only to the remaining MC-LR in solution. Finally, total organic carbon (TOC) and inorganic ions (NO 2 -, NO 3 - and NH 4 +) determinations confirmed that complete photocatalytic mineralization of MC-LR was achieved under both UV-A and solar light. © 2011 Elsevier B.V. Source

He X.,University of Cincinnati | Pelaez M.,University of Cincinnati | Westrick J.A.,Lake Superior State University | O'Shea K.E.,Florida International University | And 6 more authors.
Water Research

The destruction of the commonly found cyanobacterial toxin, microcystin-LR (MC-LR), in surface waters by UV-C/H 2O 2 advanced oxidation process (AOP) was studied. Experiments were carried out in a bench scale photochemical apparatus with low pressure mercury vapor germicidal lamps emitting at 253.7nm. The degradation of MC-LR was a function of UV fluence. A 93.9% removal with an initial MC-LR concentration of 1μM was achieved with a UV fluence of 80mJ/cm 2 and an initial H 2O 2 concentration of 882μM. When increasing the concentration of MC-LR only, the UV fluence-based pseudo-first order reaction rate constant generally decreased, which was probably due to the competition between by-products and MC-LR for hydroxyl radicals. An increase in H 2O 2 concentration led to higher removal efficiency; however, the effect of HO scavenging by H 2O 2 became significant for high H 2O 2 concentrations. The impact of water quality parameters, such as pH, alkalinity and the presence of natural organic matter (NOM), was also studied. Field water samples from Lake Erie, Michigan and St. Johns River, Florida were employed to evaluate the potential application of this process for the degradation of MC-LR. Results showed that the presence of both alkalinity (as 89.6-117.8mg CaCO 3/L) and NOM (as ~2 to ~9.5mg/L TOC) contributed to a significant decrease in the destruction rate of MC-LR. However, a final concentration of MC-LR bellow the guideline value of 1μg/L was still achievable under current experimental conditions when an initial MC-LR concentration of 2.5μg/L was spiked into those real water samples. © 2011 Elsevier Ltd. Source

Dimitrakopoulos I.K.,National and Kapodistrian University of Athens | Dimitrakopoulos I.K.,Institute of Physical Chemistry | Kaloudis T.S.,Laboratory Supply Company | Hiskia A.E.,Institute of Physical Chemistry | And 2 more authors.
Analytical and Bioanalytical Chemistry

Anatoxin-a is a potent alkaloid neurotoxin produced by a number of cyanobacterial species and released in freshwaters during cyanobacterial blooms. Its high toxicity is responsible for several incidents of lethal intoxications of birds and mammals around the world; therefore anatoxin-a has to be regarded as a health risk and its concentration in lakes and water reservoirs should be monitored. Phenylalanine is a natural amino acid, also present in freshwaters, isobaric to anatoxin-a, with a very similar fragmentation pattern and LC retention. Since misidentification of phenylalanine as anatoxin-a has been reported in forensic investigations, special care must be taken in order to selectively determine traces of anatoxin-a in the presence of naturally occurring phenylalanine. A fast LC tandem MS method was developed by using a 1.8 μm 50 × 2.1 mm C18 column for the separation of anatoxin-a and phenylalanine, achieving a 3-min analysis time. Isotopically labelled phenylalanine-d 5 was employed as internal standard to compensate for electrospray ion suppression and sample preconcentration losses. Both compounds were preconcentrated 1,000-fold on a porous graphitic carbon solid-phase extraction (SPE) cartridge after adjustment of sample pH to 10.5. The method was validated by using lake water spiked at four different levels from 0.01 to 1 μg L-1. Anatoxin-a recovery ranged from 73 to 97%, intra-day precision (RSD%) ranged from 4.2 to 5.9, while inter-day precision (RSD%) ranged from 4.2 to 9.1%. Limits of detection and quantification were 0.65 and 1.96 ng L-1 respectively. The method was successfully applied for the detection of anatoxin-a in Greek lakes at concentrations ranging from less than 0.6 to 9.1 ng L-1. © 2010 Springer-Verlag. Source

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